CA1289073C - Allergen absorbent and blocking gel - Google Patents
Allergen absorbent and blocking gelInfo
- Publication number
- CA1289073C CA1289073C CA000519891A CA519891A CA1289073C CA 1289073 C CA1289073 C CA 1289073C CA 000519891 A CA000519891 A CA 000519891A CA 519891 A CA519891 A CA 519891A CA 1289073 C CA1289073 C CA 1289073C
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- CA
- Canada
- Prior art keywords
- clay
- weight
- composition
- aerosol
- skin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/042—Gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
Abstract
AN ALLERGEN ABSORBENT AND BLOCKING GEL
ABSTRACT OF THE DISCLOSURE
An allergen absorbent and blocking gel for topical application to the skin comprises an organophilic clay of the smectite type and a quaternary ammonium compound, having aryl or alkyl groups in the range of from 10 to 22 carbon atoms and a vehicle comprising long-chain hydrocarbon or volatile silicone. The material can be made in the form of a stick, a salve or an aerosol spray.
It is essential that the organophilic clay gel be highly activated. This is accomplished by high-shear mixing and/or by the use of a low molecular weight polar organic dispersant, such as propylene carbonate. This can also be accomplished using self-activating and self-dispersing clays which do not require high shear or polar activators.
Application of the resulting highly-activated gel to the skin results in a blocking effect by means of the clay platelets and an absorption and retention of the urushiol oil allergen in the active tallow tails of the alkyl groups of the quaternary ammonium compound which has been ion exchanged with the clay.
ABSTRACT OF THE DISCLOSURE
An allergen absorbent and blocking gel for topical application to the skin comprises an organophilic clay of the smectite type and a quaternary ammonium compound, having aryl or alkyl groups in the range of from 10 to 22 carbon atoms and a vehicle comprising long-chain hydrocarbon or volatile silicone. The material can be made in the form of a stick, a salve or an aerosol spray.
It is essential that the organophilic clay gel be highly activated. This is accomplished by high-shear mixing and/or by the use of a low molecular weight polar organic dispersant, such as propylene carbonate. This can also be accomplished using self-activating and self-dispersing clays which do not require high shear or polar activators.
Application of the resulting highly-activated gel to the skin results in a blocking effect by means of the clay platelets and an absorption and retention of the urushiol oil allergen in the active tallow tails of the alkyl groups of the quaternary ammonium compound which has been ion exchanged with the clay.
Description
~ 2 FIELD OF THE `INVE~TION
This invention relates to an allergen absorbent and blocking gel for topical application to the skin to prevent the allergic reaction of persons coming into 5 contact with poison ivy, poison oak or poison sumac.
BACKGROUND OF THE INVENTION
Poison ivy and poison oak are two of the major causes of allergic contact dermatitis in the United States today. According to Dr. William Epstein, as re-10 ported in the Smithsonian, Volume 16, Number 5, dated August, 1985 by Noel Vietmeyer:
"Poison ivy and poison oak are by far the major causes of allergic contact dermati~is in the United States. More people suffer from them than from all the other aller-gic skin diseases combined No one counts the number of cases, but there are probably at least ten million a year, nationwide.
Poison oak and poison ivy are possibly the greatest cause to workmen's disability in the nation;
each year may bring more than 140,000 cases in the workplace, causing perhaps more than 152,000 lost work days.
The allergen common to poison oak, poison ivy a~d poison sumac is a heavy oil called urushiol. It is a 30 ciear, gummy, oily substance that is so incredibly re-a~tive that only a pin-head amount can cause rashes in 500 sensitive people. Additionally, the effect of the allergen is so long lasting ~hat botanists have recei~ed serious derma~itis from plant samples stored away for 35 more than a century. In one reported incident, lacquer from a Chinese jar, which had been buried for aImost a thousand years, resulted in dermatitis. Additionallyf it does not affect animals and household pets. Cats and dogs can be exposed and actually play in the area, .
~ 7~
without being affected, but can infect their o~ners by brushing up against their skin and transferring the urushiol on their coats to the unexposed areas of the human anatomy. According to Dr. Epstein, ibid.:
I'Between 15 and 25% of us are essentially immune, 25% are mildly sensitive and don't normally develop severe reactions, 25 to 30% are moderately sensitive and break out significantly with the amount of urushiol found in one leaf and 10 to 20~ are so ex-quisitely sensitive that less than one leaf produces intense dermatitis..."
The oily substance urushiol, when in contact with the skin, penetra~es the outer skin layers and begins ~o ; chemically bind to the skin cells. The body sees the combination of ~he urushiol in chemical combination with a skin cell as a foreign intruder. The immune system 20 immediately rushes large white cells called macrophages and T-lymphocytes to destroy the affected skin cells.
Dr. Epstein explains, ibid.:
"It's the body's own over-reaction that causes the complications. In ~5 sensitized persons, the area fills up with the white blood cells and they release so much cell-destroying toxins that they tear apart even the skin itself. That's what produces 30 i the blisters and suppurating sores."
Many folk remedies have been proposed for use after t~e contact with the urushiol. These include bathing :Ln horse urine or bleach, cleaning the skin with gasoline, morphine, gun powder, buttermilk, marshmallows or ~35 strychnine; drinking photographer's hypo; or rubbing on ;amrnonia, mustard, LysoL~, hairspray, clear nail polish, meat tenderizer or toothpaste.
Drinking milk from goats that have grazed on poison ivy or poison oak has long been claimed to give immunity.
~, - -.
,: . .
. , .
According to Dr. Byers of the University of California 7 S
Dermatology Department (San Francisco), ibid.:
"This is one folk remedy that probably works, although it has never been tes~ed. There remains something magic about oral doses of urushiol oil, and goat's milk probably has traces of lt. If you drink goat's milk, you're probably doing about the same thing we are in our vaccine work."
The sores can be treated by physicians with various cortisone salves. However, it is essential that the salve be used for the term of the allergic reaction.
15 The rash immediately disappears upon application of the cortisone-containing salve, but will rebound or reappear if the treatment is stopped prior to the end of the reaction.
A major problem as to the contact with urushiol 20 from poison oak, poison sumac and poison ivy is encoun-tered by the foresters of the U. S. Forestry Service.
This is particularly severe in ~he case of forest fires, where the soot and gases from the burning flames contain urushiol, which can get onto the foresters fighting the 25 fire and even into their respiratory system, causing severe complications by swelling and closing off of the esophagus and respiratory systems.
; Work is under way at the University of Oregon and at the University of California as to developing tests 3~ to determine susceptibility to poison ivy and the other toxic plants containing urushiol. Other work i6 con-cerned with developing topical ointments, salves and other prophylactic creams or gels for the prevention of the allergic reaction through blocking of the urushiol 35 oil from contac~ with the skin. Hundreds of materials have been tested with varying results.
~8~3 ~, SUMM~RY OF THE INV~NTION
_ _ _ _ _ According to ~his invention, an allergen absorbent and blocking gel, topically applied to the skin effec-tively blocks the skin from contact with urushiol and absorbs the urushi-)l and holds it away from the skin until it is washed off with soap and water. The allergen absorbent and blocking gel comprises a highly-activated organophilic clay gellant and a long-chain hydrocarbon or volatile silicone fluid vehicle. The organophilic clay gellant consists of a smect:ite clay having a relatively high cation exchange capacity which has been exchanged with a quaternary ammonium compollnd having at least one alkyl group containing from about 10 to 22 carbon atoms. It is essential that the organophilic clay and quaternary ammonium compound be highly activated and this is accomplished by high-shear mixing with a colloid mill or other known mechanisms and the use of a low mol~cular weight polar activator. such as methanol, or a self-acti~ative material. The highly-activated gel.
consisting of platelets of ~he smectite clay. forms a barrier on the skin, possibly through contact of the active tallow tails of the organic material with the lipids of the skin and by absorption of the urushiol in the organic tallow ~ails. It is felt, therefore, that there is a partitionin~ effect which effectively blocks and absorbs the oil phase urushiol from aqueous phase perspiration and the like, allowing the urushiol to be held away from the skin and held in chemical combination with'the reactive tallow tails of the organo-treated clay gel, while allowing the aqueous phase materials to pass through the clay barrier.
'.
' -4a-Thus, the allergen absorbent and blocking composition may be topically applied to the skin and clothes and thereby effectively blocks the skin and adjacent cloth from contact with urushiol and absorbs the urushiol and holds it away from the skin until it is washed off with soap and water.
~ESCRIPTION OF l'HE DR~WINGS
~ ig. 1 is a diagramma~-ic view of the skin's sur~ace and the organophilic clay platelets actin~ as a barrier to the invading urushiol droplets.
~r~
~X8~ 3 Fig. 2 is a diagrammatic view of an individual clay platelet with the alkyl groups attached thereto.
DESCRTIPTION OF THE PREFERRED EMBDIMENT
I~ has been known for a long time that organic compounds which contain a cation will react under favourable conditions by ion exchange with clays which contain a negative layer-lattice and exchangeable cations to form organophili~ organic-clay products. If the organic cation contains at least one a:Lkyl containing at least 10 carbon atoms, then such organo-clays have the property of swelling in certain organic liquids. See, for example, U. S. Patent Number 2,531,427 and U. S. Patent Number 2,966,506. See also the book_Clay Mineraloqy ~Second Edition, 1968, by Ralph E. Grim ~McGraw-Hill Book Co., Inc.), particularly Chapter 10, "Clay-~ineral -Organic Reactions," pp. 356-368 - "Ionic Reactions, Smectite;" and pp. 392-401 ~ "Organophilic Clay-Mineral Complexes." Since the commercial introduction of these organo-clays in the early '50's, it has become well-known to gain maximum gelling (thickening) by adding a low molecular weight polar organic compound to the composition. Such polar organic compounds have been variously called activators, dispersion aids, solvating agents, and the like. See, for example, U.S. Patent Numbers 2,677,661, O'Halloran; 2,704,276, McCarthy, et al;
This invention relates to an allergen absorbent and blocking gel for topical application to the skin to prevent the allergic reaction of persons coming into 5 contact with poison ivy, poison oak or poison sumac.
BACKGROUND OF THE INVENTION
Poison ivy and poison oak are two of the major causes of allergic contact dermatitis in the United States today. According to Dr. William Epstein, as re-10 ported in the Smithsonian, Volume 16, Number 5, dated August, 1985 by Noel Vietmeyer:
"Poison ivy and poison oak are by far the major causes of allergic contact dermati~is in the United States. More people suffer from them than from all the other aller-gic skin diseases combined No one counts the number of cases, but there are probably at least ten million a year, nationwide.
Poison oak and poison ivy are possibly the greatest cause to workmen's disability in the nation;
each year may bring more than 140,000 cases in the workplace, causing perhaps more than 152,000 lost work days.
The allergen common to poison oak, poison ivy a~d poison sumac is a heavy oil called urushiol. It is a 30 ciear, gummy, oily substance that is so incredibly re-a~tive that only a pin-head amount can cause rashes in 500 sensitive people. Additionally, the effect of the allergen is so long lasting ~hat botanists have recei~ed serious derma~itis from plant samples stored away for 35 more than a century. In one reported incident, lacquer from a Chinese jar, which had been buried for aImost a thousand years, resulted in dermatitis. Additionallyf it does not affect animals and household pets. Cats and dogs can be exposed and actually play in the area, .
~ 7~
without being affected, but can infect their o~ners by brushing up against their skin and transferring the urushiol on their coats to the unexposed areas of the human anatomy. According to Dr. Epstein, ibid.:
I'Between 15 and 25% of us are essentially immune, 25% are mildly sensitive and don't normally develop severe reactions, 25 to 30% are moderately sensitive and break out significantly with the amount of urushiol found in one leaf and 10 to 20~ are so ex-quisitely sensitive that less than one leaf produces intense dermatitis..."
The oily substance urushiol, when in contact with the skin, penetra~es the outer skin layers and begins ~o ; chemically bind to the skin cells. The body sees the combination of ~he urushiol in chemical combination with a skin cell as a foreign intruder. The immune system 20 immediately rushes large white cells called macrophages and T-lymphocytes to destroy the affected skin cells.
Dr. Epstein explains, ibid.:
"It's the body's own over-reaction that causes the complications. In ~5 sensitized persons, the area fills up with the white blood cells and they release so much cell-destroying toxins that they tear apart even the skin itself. That's what produces 30 i the blisters and suppurating sores."
Many folk remedies have been proposed for use after t~e contact with the urushiol. These include bathing :Ln horse urine or bleach, cleaning the skin with gasoline, morphine, gun powder, buttermilk, marshmallows or ~35 strychnine; drinking photographer's hypo; or rubbing on ;amrnonia, mustard, LysoL~, hairspray, clear nail polish, meat tenderizer or toothpaste.
Drinking milk from goats that have grazed on poison ivy or poison oak has long been claimed to give immunity.
~, - -.
,: . .
. , .
According to Dr. Byers of the University of California 7 S
Dermatology Department (San Francisco), ibid.:
"This is one folk remedy that probably works, although it has never been tes~ed. There remains something magic about oral doses of urushiol oil, and goat's milk probably has traces of lt. If you drink goat's milk, you're probably doing about the same thing we are in our vaccine work."
The sores can be treated by physicians with various cortisone salves. However, it is essential that the salve be used for the term of the allergic reaction.
15 The rash immediately disappears upon application of the cortisone-containing salve, but will rebound or reappear if the treatment is stopped prior to the end of the reaction.
A major problem as to the contact with urushiol 20 from poison oak, poison sumac and poison ivy is encoun-tered by the foresters of the U. S. Forestry Service.
This is particularly severe in ~he case of forest fires, where the soot and gases from the burning flames contain urushiol, which can get onto the foresters fighting the 25 fire and even into their respiratory system, causing severe complications by swelling and closing off of the esophagus and respiratory systems.
; Work is under way at the University of Oregon and at the University of California as to developing tests 3~ to determine susceptibility to poison ivy and the other toxic plants containing urushiol. Other work i6 con-cerned with developing topical ointments, salves and other prophylactic creams or gels for the prevention of the allergic reaction through blocking of the urushiol 35 oil from contac~ with the skin. Hundreds of materials have been tested with varying results.
~8~3 ~, SUMM~RY OF THE INV~NTION
_ _ _ _ _ According to ~his invention, an allergen absorbent and blocking gel, topically applied to the skin effec-tively blocks the skin from contact with urushiol and absorbs the urushi-)l and holds it away from the skin until it is washed off with soap and water. The allergen absorbent and blocking gel comprises a highly-activated organophilic clay gellant and a long-chain hydrocarbon or volatile silicone fluid vehicle. The organophilic clay gellant consists of a smect:ite clay having a relatively high cation exchange capacity which has been exchanged with a quaternary ammonium compollnd having at least one alkyl group containing from about 10 to 22 carbon atoms. It is essential that the organophilic clay and quaternary ammonium compound be highly activated and this is accomplished by high-shear mixing with a colloid mill or other known mechanisms and the use of a low mol~cular weight polar activator. such as methanol, or a self-acti~ative material. The highly-activated gel.
consisting of platelets of ~he smectite clay. forms a barrier on the skin, possibly through contact of the active tallow tails of the organic material with the lipids of the skin and by absorption of the urushiol in the organic tallow ~ails. It is felt, therefore, that there is a partitionin~ effect which effectively blocks and absorbs the oil phase urushiol from aqueous phase perspiration and the like, allowing the urushiol to be held away from the skin and held in chemical combination with'the reactive tallow tails of the organo-treated clay gel, while allowing the aqueous phase materials to pass through the clay barrier.
'.
' -4a-Thus, the allergen absorbent and blocking composition may be topically applied to the skin and clothes and thereby effectively blocks the skin and adjacent cloth from contact with urushiol and absorbs the urushiol and holds it away from the skin until it is washed off with soap and water.
~ESCRIPTION OF l'HE DR~WINGS
~ ig. 1 is a diagramma~-ic view of the skin's sur~ace and the organophilic clay platelets actin~ as a barrier to the invading urushiol droplets.
~r~
~X8~ 3 Fig. 2 is a diagrammatic view of an individual clay platelet with the alkyl groups attached thereto.
DESCRTIPTION OF THE PREFERRED EMBDIMENT
I~ has been known for a long time that organic compounds which contain a cation will react under favourable conditions by ion exchange with clays which contain a negative layer-lattice and exchangeable cations to form organophili~ organic-clay products. If the organic cation contains at least one a:Lkyl containing at least 10 carbon atoms, then such organo-clays have the property of swelling in certain organic liquids. See, for example, U. S. Patent Number 2,531,427 and U. S. Patent Number 2,966,506. See also the book_Clay Mineraloqy ~Second Edition, 1968, by Ralph E. Grim ~McGraw-Hill Book Co., Inc.), particularly Chapter 10, "Clay-~ineral -Organic Reactions," pp. 356-368 - "Ionic Reactions, Smectite;" and pp. 392-401 ~ "Organophilic Clay-Mineral Complexes." Since the commercial introduction of these organo-clays in the early '50's, it has become well-known to gain maximum gelling (thickening) by adding a low molecular weight polar organic compound to the composition. Such polar organic compounds have been variously called activators, dispersion aids, solvating agents, and the like. See, for example, U.S. Patent Numbers 2,677,661, O'Halloran; 2,704,276, McCarthy, et al;
2,833,720, Stratton; 2,979,229, Stratton; and 3,294,683, Stansfield, et al. The most efficient and accepted polar materials for use as activators have b~en found to be low Imolecular weight alcohols and ketones, particularly methanol and acetone. The activators, however, have very low flash points and require the use of flame-proof apparatus. Higher-boiling activators, having higher flash points, such as propylene carbonate, may also be used.
'128~ 3 Clays used to prepare the allergen absorbent and blocking gels of this invention are the smectite-type clays, having a high cation exchange capacity. The cation exchange capacity of the smectite clay should equal or exceed 50 milliequivalents per 100 grams of clay. Particularly desirable types of clay are the naturally-occurring Wyoming variety of swelling bentonite and like clays, as well as hectorite, a swelling magnesium-lithium silicate clay. Suitable bentonite clays are also found in Europe, particularly in the Moosburg section of Bavaria, near Munich. Smectite clays can also be prepared synthetically by either a pneumatolytic or preferably a hydrothermal synthesis process. Representative hydrothermal processes for preparing synthetic smectities are prepared in the following U. S. Patent Numbers: U. S. Pater.t Number 3,252,757 Gransuist; U. S. Patent Nu~ber 3,586,478, Neumann; U. S. Patent Number 3,666,407, Orelemann; U.S.
Patent Number 3,671,190, Neumann; U. S. Patent Nu~ber 3,844,978, Hickson; U. S. Patent Number 3,844,979, Hickson; ~. S. Patent Number 3,852,405, Granquist; and U. S. Patent Number 3,8~5,147, ~ranquist.
As has been previously indicated, the invention relates to the discovery that organo-treated clays of the smectite type, which are highly activated, produce allergen absorbents and blocking gels for topical application to the skin to prevent contact of the skin with the allergens produced by poison ivy, poison oak or poison s~mac. The smectite-type clays, which have ,sufficient cation exchange capacity to be ion exchanged 3a wikh organic compounds having a cation and one or more alkyl chains, having at least 10 carbon atoms naturally occur in Wyoming and in the Moosburg section !O' f Bavaria, ~ 3 in the vicinity of Munich, Germany. The clays are of the bentonite type and are usually of ~he sodium form.
However, if they are not already in the sodium form, they can be converted by passing an aqueous clay slurry 5 through a bed of cation exchange resin in the sodium form. Alternately, the smectite clay can be mixed with water and a soluble sodium compound, such as sodium carbonate, sodium hydroxide and sheared at high shear in a pug mill or extruder. Additionally, smectite-type 10 clays can be prepared. synthetically, either by a pneumato-lytic, or preferably a hydrothermal, synthesis process.
Representatives of such smectite clays are the following:
Montmorillonite [(A14 ~Mgx) si3~2o(oH)4 - fFf]x R where 0.55 _ 15 x <- 1.10, f ~ 4 and R is selected from the group con-sisting of Na, Li, NH4, and mixtures thereof;
Bentonite r(A14 - xMgx(Si8 - yAly)O20~OH~ - fFf](x+y) R where 0 < x < 1.10, 0 ~ y < 1.10, 0.55 < (x+y) < l.lV, f -< 4 20 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof Beidellite [(A14 + y) (Si8 - yAly)O20(OH)4 - ~Ff]x R where 0.55 -< x < 1.10, 0 ~ y < 0.44, f ~ 4 and R is selected 25 from the group consisting of Na, Li, ~H4, and mixtures thereof;
Hectorite g6 xLix)Si820(OH)4 ~ fF:E]X R+ where 0.57 <
x ~ l.lS, f < 4 and is selected from the group consisting 30 of Na, Li, NH~, and mixtures thereof;
Saponite [(Mg6 ~ yAly) (Si8 - x ~ 6Alx-~y)20( )~ f ~
where 0.58 < x < 1.18, 0 < y <. 0.66, f < 4 and R+ is selected from the group consisting of.Na, Li, NH4, and 35 mixtures thereof;
: - ~
.
~ 3 Stevensite [(Mg6 ~ Al )Si8O20(OH)4 - fFfl2 x R~ where 0 28 <
x < 0.57, f < 4 and R is selected from the group con-sisting of Na, Li, NH4, and mixtures thereof.
These smectite clays may be synthesized hydrother-mally by forming an aqueous reaction mixture in the form of a slurry containing mixed hydrous oxides or hydroxides of the desired metals with or without, as the case may be, sodium (or alternate exchangeable cation or mixture lO thereo~) fluoride in the proportions defined in the above formulas and preselected values of x, y and f for the particular synthetic smectite desired. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature within the range of approxi-15 mately 100 to 325C, preferably 275 to 300C for asufficient period of time to form the desired product.
Formulation times of 3 to 48 hours are typical at 300C, depending on the particular smectite being synthesized ~nd the optimum time can be readily determined by pilot 20 triaIs. The organic compounds useful in this invention are quaternary and ammonium salts containing one methyl radical or one benzyl radical and a mixture of trialkyl radicals, having from 14 to 20 carbon atoms, preferably wherein 20 to 35% have 16 carbon atoms and 5% have 18 25 cjarbon atoms on a 100% basis. The anion salt is prefer-ably selected from the group consisting of chloride and bromide and mixtures thereof and is preferably a chlori.de.
However, other anions, such as acetate, hydroxide, nitrite, etc., may be present in the ammonium salt to 30 neutralize the quaternary ammonium compound. The methyl or benzyl triàlkyl ammonium salt may be represented as ~ollows:
' :
: ; ' ` ,' ';~. `
.
-~28~7~
r I 1 1 +
___ _ , The preEerred quaternary amine for use in the practice of this invention is dimethyl dihydrogenated t~llow ammonium chloride. Rl can be methyl or benzyl, ; R2 can be me~hyl or C10 to C18. R3 can be methyl or ClO
5 to Cl8- R4 can be C10 to Cl~. Commercially prepa hydrogena~ed tallow typically analyzes 2.0% C14, 0.5%
15' 9-0% C16~ 1-5% C17~ 66-0% Clg and 1.0% C20 alkyl radicals.
Nevertheless, the alkyl radicals may be derived 10 from o~her natural oils, including various vegetable oils, such as corn oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils ~j and fats. Additionally, the alkyl radicals may be petrochemically derived, as from alpha olefins.
We have found that it is essential that the organo-philic clay compounds be highly activated. Alternately, self-activating organophilic clays may be used which do not require activation with polar materials. Activation of the organophilic clays may be accomplished by use of 20 organic polar materials of low molecular weight (which are known as activators). The most efficient and accepted polar materials are low molecular weight alcohols and ketones, particularly methanol and acetone.
However, these activators do have the disadvantage of a 25 very low flash point and therefore the danger of com-bustion is present. Higher boiling flash point , ' : . .
~73 activators, such as propylene carbonate, therefore, may be advantageously utilized. The organophilic clays are prepared by admixing the smec~ite clay, the quaternary ammonium compound and water together, preferably at 5 temperatures within the range of 100 to 180F (38 to 77C) for a period of time sufficient for the organic compound to coat the smectite clay particle, follo~ed by filtering, washing, drying and grinding. In using the organophilic clays in emulsions, the drying and 10 grinding steps can be eliminated. When the smectite clay and quaternary ammonium compound and water are mixed together in such concentrations that a slurry is not formed, then the filtration and washing steps are eliminated. Preferably, however, the smectite clay is 15 dispersed in water at a concentration of from about 3 to 7% and the slurry is optionally c~ntrifuged to remove nonclay impurities. These nonclay impurities may con-stitute between about 10 to 50% of the starting clay composition. Thereafter, the slurry is agitated and 20 heated to a temperature in the range of 104 to 170~F
(60 to 77C), the quaternary amine salt added in the proper milliequivalent ratio, pre~erably as a liquid in isopropanol. The amount of the quaternary ammonium salt added to the smectite clay for purposes of this invention 25 m~st be sufficient to impart ~o the organophilic clay the enhanced dispersion characteristics desired. Milli-e~uival.ent ratio is defined as the number of milli-equivalents of the organic compound in the organo-clay per 100 grams oE clay, on a 100% active clay basis. The 30 organophilic clays preferably have a milliequivalent ratio of from 100 to 120. However, if polar organic activators are utilized, a much lower milliequivalent ratio can be utilized without affecting the resultant gel system disadvantageously. The smectite clay and 35 quaternary ammonium compoundare admi~ed with a hydrocarbon ., ~ -.,. .~ .
~ 7'3 vehicle or a volatile silicone vehicle and the entire admi~ture is subjected to a high shear mixing in a colloid mill or the like. Generally speaking, the con-centration of the organo-treated clay is in the ratio of 5 from 5 to 15% by weight. Therefore, the vehicle for the resulting gel makes up the balance of the mixture in the weight concentration of from about 99 to 85%.
The admixture can be used in the form of a salve in which the concentration of the organo-treated clay is in 10 the range of 10 to 12% by weight. If the gel is utilized in the form of an aerospray, the admixture of organo-treated clay forming the gel is in the ratio of 5 to 10%
and the total gel makes up about 30% of the contents of the can, with the rest of the materiaL being a propellant.
15 Typical aerosol propellants are hydrocarbon blends of isobutane. The trade designations are A46~, A31~ and A70~. If the allergen absorbent and blocking gel is desired to be formulated in the form of a stick, the con-centration of the organo-treated clay should consist of 20 about 15 to 20% and the hydrocarbon vehicle making up the balance. In this condition, the material is in the form of the well-known sticks, such as are used in stick deodorants and can be applied to the skin merely by ; wiping the stick, in its container, over the area to be 25 protected.
DESCRIPTION OF THE DRA:WING
_ .
~ Referring now to Fig. 1 J there is illustrated a diagrammatic section of the skin af-ter a diagram of Gray's natomy. As will be noted, the skin is made up 30 of an epidermis 1 and a dermis 7. The epidermis consists of five layers, the stratum corneum 2, the stratum lucideum 3, -the s-tratum granulosum ~, the stratum mucosum 5, which terminates in the stratum germinationium 6. The sudoriferous gland 8 is located in the dermis.
35 However, the ducts 9 extend through the epidermis to the ~ .
.
~2~ 73 outer layer of the skin. Additionally, the shaft of the hair 10 extends through duct 14 and t~rminates at the bulb 12. The hair follicle is surrounded by sebaceous glands 11, which discharge into the duct 14 to ~eep the hair shaf~ lubricated. Additionally, the dermis / con-tains a grea~ deal of adipose tissue 2~ and some relative-ly deep-lying arteries 21 and nerves 22.
According to the drawin~, the or~ano-treated clay 15, made up of platelets 16 and the depending tallow tails 17 formas a layer over the skin with the ~allow tails re-acting to some extent with the lipids of the skin's s~rEace. This allows the platelets to alLgn themsetves pretty much as a shield against the invndin~ urushiol droplets lB. Stroking cf the platele~s manually appears to orient t~e platelets so as to lie parallel with the epidermal cells oE the skin. T~e urushiol droplets, in order to reach the skin must pass through the barriers or blockers form~d by the platelets 16 without being absorbed by the reactive organic alkyl groups in the form o~ ~allow tails 17. It is believed that the tallow tails, through the van-der Waal forces, tend to absorb che~ically the urushiol droplets and hold the urushiol droplets and thus prevent their contact with the skin (see Fig.~ 2). Any urushiol droplets which might escape the first row o~ tallow taiLs are blocked by the clay pla~elets 16 and then encounter succeeding alkyl groups where absorption ~akes placc.
Additionally, the organophilic clay aerosol composition can be sprayed onto the clothes or tools, so as to suspend and inactivate the allergen until the clothes or tools can be laundered.
Otherwise, there is some danger that other persons can be exposed to the allergen when these are laundered or that the worker himself may be reexposed by contact with the unwashed clothes at a later time.
~2~
~12a-Urushiol 18 is diagrammatically illustrated in Fig. 2, according to i~s chemical formula. As will be no~ed, the urushiol compound consists of a phenyl group 20 with two hydrogen groups and a long hydrocarbon chain of 15 to 17 carbons, designated as 19.
Additionaliy, the quaternary ammonium compounds are designated with the tallow tails 17, consisting of 16 to 18 carbons. Some of the quaternary am~nium compounds contain a benzyl compound 21 and one alkyl chain and two methyl groups, while the other quaternary ammonium com-pounds consist oF two alkyl hydrocarbon chains 1/ and two .
,, - .
, ' ' ' ~28~ 3 methyl groups. The van-der Waal bonding of the hydro-carbon chain 19 of the urushiol compound 18 is dia~ram-matically shown with the long-chain alkyl group l7 of the organophilic clay ]5. Additionally, i~ is felt th~t the phenyl group 20 of the urushiol compound may have some affinity for the active surface of the platelet 1~
of ~he organophilic clay. This is shown diagramma~ically in the right-hand portion of Fig. ~.
It should be un~erstood that this explanatiotl is som~what hypothetical. However, it ;s support~d by data, as will hereinafter be shown. The fact of the matter is that adsorption apparently is not the major mechanism itl ~his instance, since materials with higher surface areas do not provide the protection that is provided by the organo-treated clays~ It ~s felt, the~efore, that the organic surface area is of major importance while the inorganic surface area formed by the pores oE t~e clay platel~s per~orm only a secondary function r~lativ~
to ~he absorp~ive function performed by th~ r~ctive tallow tails of the organophilic clays.
T~e invention will be better understood by rererence to the examples contained hereinafter.
In the following examples, reference is made to Sure~
deodorant and DrysolTM, both of which contain the antiperspirant aluminum chlorohydrate.
IThe Sur ~ antiperspirant, in the spray form, contains aluminum chlorohydrate, cyclomethicone, ~uaternium-18 hectorite, per~ume, ethanol, isobutane and propane. This composition is reported to contain from 1 to 5~ guaternium-18 hectorite. See, for example~ Clinical Toxicoloq~ of Commercial Products, Gosselin, et al, 5th edition, William and Watkinsr 1984, PV-633.
B
.
.
, . .
~2~ '73 -13a-Quaternium-18 hectorite is a reaction product of hectorite and ~uaternium-18 is commercially availa~le as Bentone 38 (NL Chemicals). Quaternium-18 (CAS Number 61789-80-8) is predominantly (90 to 100%) a quaternary salt that conforms generally to the formula:
CH3 ~
R C - R Cl where R represents hydrogenated tallow fatty radicals.
~ uatern~um-18, quaternium-18 hectorite and quaternium-18 bentonite are generally considered safe as cosmetic ingredients and have been widely used as suspending agents for antiperspirants. See ~Final Report on the Safety Assessment of Quaternium-18, Quaterniu~-18 ~ectorite, and Quaternium-18 Bentonite," ~ournal Qf the ~merican ~ollQae of ~oxic~looY, Vol. 1(2), 1982, pp. 71-83.
.
_ -14-~XAMPLF, 1 A batch of organophilic clay is prepared by admixing finely milled sodium bentonite with sufficient quaternary ammonium compound ~o as to provide 8S ~illiequivalents of quaternary ammonium compound per 100 grams of clay. The quaternary ammonium compound i~ obtained from hydrogenated tallow and contains two alXyl groups containing from 16 to 18 carbons in length and 2 methyl groups. This is commonly referred to as quaternium-18. The quaternary ammonium compound was mixed with su~ficient water and the sodium bentonite so as to produce a slurry containing about 4~ by weight of clay. The temperature of the slurry was maintained at 170 for a period of about 30 minutes. This allowed the quaternary ammonium compound to ion exchange with the clay particles. The ~lurry was then ~pray dried i~to a fine powd r. This product ~ 6 known in the cosmetic industry as quaternium-18 bentonite. The powdered organo-clay was admixed with about 4.3~ by weight of an SD-~0 alcohol and about 84% by weight of cyclomethicone (Dow-Corning 344~ as a Yehicle. This then produced a gel containing 11. 3~ oxgano-clay, 84% cyclomethicone and 4.3~ SD-40 alcohol. The gel was then loaded into an aerosol container at room temperature. A valve assem~ly was ~nserted into thè container and the val~e was crimped. An A-46 mixed hydrocarbon propel}ant was then introduced through the valve assembly under pressure to produce an aerosol composition within the can of 30:70 weight ratio o~
gel to propellant. The A~46 propellant is 84% isobutane and 16% propane by weight and has a vapor pressure of 46 psig at 70~F.
,~
B
.
~2~
-14a~
EXAMPLE _ The test procedure* involved the application of Sure~
deodorant as a comparison composition and the organophilic clay of Example 1, spray applied to the skin of the forearm at 1, 4 and 24 hours before the application of dilutions of purified urushiol in acetone in a double-blind fashion. Three samples of urushiol in acetone were made up with five microliters of urushiol in acetone, ranging i~ amount from .25ug to .OOSug. The samples of urushiol in ac'etone were then applied to the patch test sites. The p~tch test sites were thereafter read two to five days later and recorded from N to 4 as follows:
N = Normal 1 = Erythema and edema involving half the test. site 2 = Erythema and edema plus small vesicles involving the entire site 3 = Full involvement of the test site with erythema and ed~ma and large vesicles 4 = Bullae ~ -A -1 score equals a de~inite positive reaction which in-volves less than 1/2 of the test site and a ~ equals a questionable reaction which either is subsequen~ly read as + or *T~ese tests were conducted under a grant from the U.S.
Forestry Service under the supervision of Dr. William Epstein of the University ~f California Medical School at San Francisco.
~' :
. ~
' ~ ~
~' ~
A second preliminary study was car~ied QUt, com~
paring the results of pretreatment wit~ Sure~ to pre-treatment with Drysol~ (a 20% w/v concentrate of 5 aluminum chloride he~ahydrate in alcohol). The pre-treatment time was 4 hours. The patch tests were urushiol and the patch test readings were the same as described above.
EXAMPLE _ In the next series of experiments, the subjects were pretreated with breakdown products of Sure~ that either were missing the aluminum ,chlora,lhydrate or the suspending agents (hectorite and propylene carbonate).
The patch tests with urushiol and the patch test readings 15 were the same as described above.
The results of these tests are shown in Table I, T~BL~ I
Average Protective Effect of SURE~ and Example 1 Compared to the Control 20 Pretreatment ' ' Time'' Mi'c'rogr'a'm'Di'lut'i'o'n's''o'f'Urush'i'ol .
l hour 0.25 '0'.1 '0'.'05 '0'.'025 Sure~ 1 1.3 ,1.2 ,1.0 Example 1 N o t D o n e 25 4;hours Sure~ 1.5 0.9 0.9 0.5 ' Example 1 3.0 2.0,1.8 1~3 -~
24 h'ours Sure~ 0 0.751.0 0.4 30 Example 1 1.5 0.9 0.9 1.5 Table I shows that pretreatment with the Sure~
deodorant does reduce the pat,ch test reaction to dilu-tions of urushiol. However, Sure~ is not able to com-pletely prevent the reactions, but simply reduce them.
35 The material of Example 1, on the other hand, was more : , . . .
- , . ~ .
. ;; . '. ~ ~; ' . .
:. . . .
'7 -16~
effective at reducing the reactions and this was par-ticularly noticeable at 4 and 24 hours after applicatio~s, as compared to Sure~. This table a~erages overa~l responses.
The preliminary study9 comparing the high concen-tration of the aluminum salt (Drysol~) to Sure~, indi-cated that the alcoholic solution was less effective than Sure~.
Another experiment compared the blocking effect of 10 Sure~ with its ingredients, i.e. without fillers and without aluminum chloralhydrate. In one instance, Sure~
was compared to the aluminum compound containing prep-aration without the fillers, i.e. ~he organophilic hectorite, and the two were equal on two occasions.
15 Sure~ was more effective in one and definitely more effective in four instances. In no instance was the aluminum salt more effective than Sure~. Sure~, con-; taining only the fillers and no aluminum was compared to Sure~ and the two preparations were e~ual on two 20 occasions. Sure~ was more effective than the fillerpreparations on two occasions and much more effec~ive on one occasion. On the other hand, the filler was more effective than Sure~ on two occasions. Finally, in direct comparison of the filler versus the aluminum 25 preparation, the filler was more effective than the aluminum salt on two occasions and much more effective in four additional trials. In one instance, the aluminum ; salt was more efEecti~e than the filler preparations.
The tests, as previously described, were carried out with three particularly sensitive individuals.
These are shown in Tables II, III and IV.
As can be seen, a~ter the second day, the control showed a normal reaction for the patch test for the low 35 concentrations, but a 2 reaction as to any concentration ~. .
.: - . .
:
..
: .
:
TABIE II
4 hours after application Day 2 Day 4 Reg.
Urushiol Control Sure~ Ex. 1 Con~rol Sùre~ Ex. 1 .25 2-1 N 3 3 N
.1 21 N 2 1 N
.05 2'N N 2 N N
.025 NN N N N N
.01 NN N N N N
24 hours after application 'Day 2 ' Day 4 Reg.
Urushi'ol Contr'ol 'Sure~ Ex. 1 'Cont'rol' S'ure~ E'x.' 1 .25 21 N 3 3 .l 21 N 2 .05 2N N 2 N N
.025 NN N N N N
.01 NN N N N N
,. , . : .
.
, ' ' .. .. .
.
` TABLE`'III
4 hours after application ''Day 2 ''Day 4 Reg.
S Urushiol 'Con'trlol `Sure~ ` Ex.` 1 ''Co`nt'rol''S`ure~''EX.',l .25 ~1 2 2 N 4 2 N
.05 2 2 N 3 2 N
.025 1 -1 N 2 1 N
.01 -1 N N N N N
24 hours a~ter application Day 2 ''Day 4 Reg. ~ , Urushiol Control Sure~ EX. 1 ~Control':Sure~ EX. 1 .25 .1 2 2 2 4 2 2 .05 2 2 2 3 2 2 .025 1 1 N 2 1 N ,~
.01 -1 N N N N N
'.
:
- : . .: :
:
,~ . .
- . ~
: . ' ' , " ~ ':
.
.~ . . . .
, ''T~B~E'IV
4 hours after application Day 2 ''Day 4 Reg.
Urus'hiol Control Su`re~''EX. 1 ` Con'trol' Sure~ Ex.' 1 .05 2 2 N 3 2 -1 .025 N N N 1 N N
.01 N N N N N N
24 hours after application Day 2 `':a'y'4 Uru_hiol Control' Sure~''EX.' 1 Con~rol' Sur'e~ 'Ex` 1 .05 2 1 1 3 2 2 .025 N -1 N 1 N N
.01 N N N N N N
i . ~. ~ ' ' ' . . . ' '- '.
~. ~ . : , ` ' `
, : ` ;. ' ,' ' , ' of urushiol above .05 micro~rams. Sure~, on the other hand, provided some protection at .05 micrograms and reduced the size of the reaction as to the concentra-tions above .l. The material of Example l, however, 5 showed full protection 4 hours after application for all concentrations of the material. Essentially the same results were obtained after Day 4. Except with the control, the severity of the reactions increased. The severity of the reaction of the high concentration of 10 urushiol increased with the Sure~ application, but the material of Example 1 gave full protection throughout the total range o-f concentration. 24 hours after appli-cation, essentially the same results were obtained on Day 2. On Day 4, the severity of -the reaction was 15 greater with the control and with the Sure~ sample and there was a 1 range of reaction for the Example 1 material after 24 hours.
Table III, for a completely different individual, who was extremely sensitive, demonstrated a more severe 20 reaction with both the control sample and the Sure~
sample, after Day 2 and Day 4, as compared to Table II.
However, the organophilic clay of Example 1 provided good protection, both for Day 2 and Day 4 throughout the entire range of urushiol concentrations. The 25 severity of the reactions increased across the board after application and e~en the material of Example 2 s~owed a moderate grade 2 reaction for the higher con-centrations a~te~ the second and fourth days. The superiority of the material of Example 1 over the control 30 and over the Sure~ is shown, however, throughout.
Table I~ demonstrates in like manner the protection afforded by the individual throughout a smaller range of urushiol concentrations. After the fourth day, from 4 hours after application, the material of Example 1 showed 35 a positive reaction, as indicated by -1. In like manner, ~
~:
-, - ' ~ ' : .
~A~1:3~ ~
the table demonstrates that even 24 hours a~ter appli-cation, there is protection against the low concentrations of urushiol by the organophilic clay of Example l on the second and fourth days following application.
A series of other over-the co~mter preparations, Technu~, Less Ivy~, and Off~, were completely ineffective in protecting the skin from the ef~ects o:E urushiol.
It is believed that the long Cl8 chain ofthe urushiol molecule is absorbed through van-der Waal forces with lO the long, Cl6 to C22 carbon tallow tails of the organo-philic clays. Additionally, it is ~elt that the phenyl group of the urushiol may have some affinity for the active surface of the clay platelet itself. The material may be applied in aerosol form, as a salve, or as a 15 stick, onto the skin, prior to encountering the urushiol-producing plants, such as poison ivy, oak or sumac. The comparative study, however, has clearly sho~n that the organophilic clays of this invention are more effective than any material heretofore known in the prevention of 20 experimentally-induced poison oak or ivy dermatitis.
Many modifications will occur to those skilled in the art from the disclosure, which is meant to be non-limiting except so as to be commensurate in scope with the appended claims.
'128~ 3 Clays used to prepare the allergen absorbent and blocking gels of this invention are the smectite-type clays, having a high cation exchange capacity. The cation exchange capacity of the smectite clay should equal or exceed 50 milliequivalents per 100 grams of clay. Particularly desirable types of clay are the naturally-occurring Wyoming variety of swelling bentonite and like clays, as well as hectorite, a swelling magnesium-lithium silicate clay. Suitable bentonite clays are also found in Europe, particularly in the Moosburg section of Bavaria, near Munich. Smectite clays can also be prepared synthetically by either a pneumatolytic or preferably a hydrothermal synthesis process. Representative hydrothermal processes for preparing synthetic smectities are prepared in the following U. S. Patent Numbers: U. S. Pater.t Number 3,252,757 Gransuist; U. S. Patent Nu~ber 3,586,478, Neumann; U. S. Patent Number 3,666,407, Orelemann; U.S.
Patent Number 3,671,190, Neumann; U. S. Patent Nu~ber 3,844,978, Hickson; U. S. Patent Number 3,844,979, Hickson; ~. S. Patent Number 3,852,405, Granquist; and U. S. Patent Number 3,8~5,147, ~ranquist.
As has been previously indicated, the invention relates to the discovery that organo-treated clays of the smectite type, which are highly activated, produce allergen absorbents and blocking gels for topical application to the skin to prevent contact of the skin with the allergens produced by poison ivy, poison oak or poison s~mac. The smectite-type clays, which have ,sufficient cation exchange capacity to be ion exchanged 3a wikh organic compounds having a cation and one or more alkyl chains, having at least 10 carbon atoms naturally occur in Wyoming and in the Moosburg section !O' f Bavaria, ~ 3 in the vicinity of Munich, Germany. The clays are of the bentonite type and are usually of ~he sodium form.
However, if they are not already in the sodium form, they can be converted by passing an aqueous clay slurry 5 through a bed of cation exchange resin in the sodium form. Alternately, the smectite clay can be mixed with water and a soluble sodium compound, such as sodium carbonate, sodium hydroxide and sheared at high shear in a pug mill or extruder. Additionally, smectite-type 10 clays can be prepared. synthetically, either by a pneumato-lytic, or preferably a hydrothermal, synthesis process.
Representatives of such smectite clays are the following:
Montmorillonite [(A14 ~Mgx) si3~2o(oH)4 - fFf]x R where 0.55 _ 15 x <- 1.10, f ~ 4 and R is selected from the group con-sisting of Na, Li, NH4, and mixtures thereof;
Bentonite r(A14 - xMgx(Si8 - yAly)O20~OH~ - fFf](x+y) R where 0 < x < 1.10, 0 ~ y < 1.10, 0.55 < (x+y) < l.lV, f -< 4 20 and R is selected from the group consisting of Na, Li, NH4, and mixtures thereof Beidellite [(A14 + y) (Si8 - yAly)O20(OH)4 - ~Ff]x R where 0.55 -< x < 1.10, 0 ~ y < 0.44, f ~ 4 and R is selected 25 from the group consisting of Na, Li, ~H4, and mixtures thereof;
Hectorite g6 xLix)Si820(OH)4 ~ fF:E]X R+ where 0.57 <
x ~ l.lS, f < 4 and is selected from the group consisting 30 of Na, Li, NH~, and mixtures thereof;
Saponite [(Mg6 ~ yAly) (Si8 - x ~ 6Alx-~y)20( )~ f ~
where 0.58 < x < 1.18, 0 < y <. 0.66, f < 4 and R+ is selected from the group consisting of.Na, Li, NH4, and 35 mixtures thereof;
: - ~
.
~ 3 Stevensite [(Mg6 ~ Al )Si8O20(OH)4 - fFfl2 x R~ where 0 28 <
x < 0.57, f < 4 and R is selected from the group con-sisting of Na, Li, NH4, and mixtures thereof.
These smectite clays may be synthesized hydrother-mally by forming an aqueous reaction mixture in the form of a slurry containing mixed hydrous oxides or hydroxides of the desired metals with or without, as the case may be, sodium (or alternate exchangeable cation or mixture lO thereo~) fluoride in the proportions defined in the above formulas and preselected values of x, y and f for the particular synthetic smectite desired. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature within the range of approxi-15 mately 100 to 325C, preferably 275 to 300C for asufficient period of time to form the desired product.
Formulation times of 3 to 48 hours are typical at 300C, depending on the particular smectite being synthesized ~nd the optimum time can be readily determined by pilot 20 triaIs. The organic compounds useful in this invention are quaternary and ammonium salts containing one methyl radical or one benzyl radical and a mixture of trialkyl radicals, having from 14 to 20 carbon atoms, preferably wherein 20 to 35% have 16 carbon atoms and 5% have 18 25 cjarbon atoms on a 100% basis. The anion salt is prefer-ably selected from the group consisting of chloride and bromide and mixtures thereof and is preferably a chlori.de.
However, other anions, such as acetate, hydroxide, nitrite, etc., may be present in the ammonium salt to 30 neutralize the quaternary ammonium compound. The methyl or benzyl triàlkyl ammonium salt may be represented as ~ollows:
' :
: ; ' ` ,' ';~. `
.
-~28~7~
r I 1 1 +
___ _ , The preEerred quaternary amine for use in the practice of this invention is dimethyl dihydrogenated t~llow ammonium chloride. Rl can be methyl or benzyl, ; R2 can be me~hyl or C10 to C18. R3 can be methyl or ClO
5 to Cl8- R4 can be C10 to Cl~. Commercially prepa hydrogena~ed tallow typically analyzes 2.0% C14, 0.5%
15' 9-0% C16~ 1-5% C17~ 66-0% Clg and 1.0% C20 alkyl radicals.
Nevertheless, the alkyl radicals may be derived 10 from o~her natural oils, including various vegetable oils, such as corn oil, soybean oil, cottonseed oil, castor oil and the like, as well as various animal oils ~j and fats. Additionally, the alkyl radicals may be petrochemically derived, as from alpha olefins.
We have found that it is essential that the organo-philic clay compounds be highly activated. Alternately, self-activating organophilic clays may be used which do not require activation with polar materials. Activation of the organophilic clays may be accomplished by use of 20 organic polar materials of low molecular weight (which are known as activators). The most efficient and accepted polar materials are low molecular weight alcohols and ketones, particularly methanol and acetone.
However, these activators do have the disadvantage of a 25 very low flash point and therefore the danger of com-bustion is present. Higher boiling flash point , ' : . .
~73 activators, such as propylene carbonate, therefore, may be advantageously utilized. The organophilic clays are prepared by admixing the smec~ite clay, the quaternary ammonium compound and water together, preferably at 5 temperatures within the range of 100 to 180F (38 to 77C) for a period of time sufficient for the organic compound to coat the smectite clay particle, follo~ed by filtering, washing, drying and grinding. In using the organophilic clays in emulsions, the drying and 10 grinding steps can be eliminated. When the smectite clay and quaternary ammonium compound and water are mixed together in such concentrations that a slurry is not formed, then the filtration and washing steps are eliminated. Preferably, however, the smectite clay is 15 dispersed in water at a concentration of from about 3 to 7% and the slurry is optionally c~ntrifuged to remove nonclay impurities. These nonclay impurities may con-stitute between about 10 to 50% of the starting clay composition. Thereafter, the slurry is agitated and 20 heated to a temperature in the range of 104 to 170~F
(60 to 77C), the quaternary amine salt added in the proper milliequivalent ratio, pre~erably as a liquid in isopropanol. The amount of the quaternary ammonium salt added to the smectite clay for purposes of this invention 25 m~st be sufficient to impart ~o the organophilic clay the enhanced dispersion characteristics desired. Milli-e~uival.ent ratio is defined as the number of milli-equivalents of the organic compound in the organo-clay per 100 grams oE clay, on a 100% active clay basis. The 30 organophilic clays preferably have a milliequivalent ratio of from 100 to 120. However, if polar organic activators are utilized, a much lower milliequivalent ratio can be utilized without affecting the resultant gel system disadvantageously. The smectite clay and 35 quaternary ammonium compoundare admi~ed with a hydrocarbon ., ~ -.,. .~ .
~ 7'3 vehicle or a volatile silicone vehicle and the entire admi~ture is subjected to a high shear mixing in a colloid mill or the like. Generally speaking, the con-centration of the organo-treated clay is in the ratio of 5 from 5 to 15% by weight. Therefore, the vehicle for the resulting gel makes up the balance of the mixture in the weight concentration of from about 99 to 85%.
The admixture can be used in the form of a salve in which the concentration of the organo-treated clay is in 10 the range of 10 to 12% by weight. If the gel is utilized in the form of an aerospray, the admixture of organo-treated clay forming the gel is in the ratio of 5 to 10%
and the total gel makes up about 30% of the contents of the can, with the rest of the materiaL being a propellant.
15 Typical aerosol propellants are hydrocarbon blends of isobutane. The trade designations are A46~, A31~ and A70~. If the allergen absorbent and blocking gel is desired to be formulated in the form of a stick, the con-centration of the organo-treated clay should consist of 20 about 15 to 20% and the hydrocarbon vehicle making up the balance. In this condition, the material is in the form of the well-known sticks, such as are used in stick deodorants and can be applied to the skin merely by ; wiping the stick, in its container, over the area to be 25 protected.
DESCRIPTION OF THE DRA:WING
_ .
~ Referring now to Fig. 1 J there is illustrated a diagrammatic section of the skin af-ter a diagram of Gray's natomy. As will be noted, the skin is made up 30 of an epidermis 1 and a dermis 7. The epidermis consists of five layers, the stratum corneum 2, the stratum lucideum 3, -the s-tratum granulosum ~, the stratum mucosum 5, which terminates in the stratum germinationium 6. The sudoriferous gland 8 is located in the dermis.
35 However, the ducts 9 extend through the epidermis to the ~ .
.
~2~ 73 outer layer of the skin. Additionally, the shaft of the hair 10 extends through duct 14 and t~rminates at the bulb 12. The hair follicle is surrounded by sebaceous glands 11, which discharge into the duct 14 to ~eep the hair shaf~ lubricated. Additionally, the dermis / con-tains a grea~ deal of adipose tissue 2~ and some relative-ly deep-lying arteries 21 and nerves 22.
According to the drawin~, the or~ano-treated clay 15, made up of platelets 16 and the depending tallow tails 17 formas a layer over the skin with the ~allow tails re-acting to some extent with the lipids of the skin's s~rEace. This allows the platelets to alLgn themsetves pretty much as a shield against the invndin~ urushiol droplets lB. Stroking cf the platele~s manually appears to orient t~e platelets so as to lie parallel with the epidermal cells oE the skin. T~e urushiol droplets, in order to reach the skin must pass through the barriers or blockers form~d by the platelets 16 without being absorbed by the reactive organic alkyl groups in the form o~ ~allow tails 17. It is believed that the tallow tails, through the van-der Waal forces, tend to absorb che~ically the urushiol droplets and hold the urushiol droplets and thus prevent their contact with the skin (see Fig.~ 2). Any urushiol droplets which might escape the first row o~ tallow taiLs are blocked by the clay pla~elets 16 and then encounter succeeding alkyl groups where absorption ~akes placc.
Additionally, the organophilic clay aerosol composition can be sprayed onto the clothes or tools, so as to suspend and inactivate the allergen until the clothes or tools can be laundered.
Otherwise, there is some danger that other persons can be exposed to the allergen when these are laundered or that the worker himself may be reexposed by contact with the unwashed clothes at a later time.
~2~
~12a-Urushiol 18 is diagrammatically illustrated in Fig. 2, according to i~s chemical formula. As will be no~ed, the urushiol compound consists of a phenyl group 20 with two hydrogen groups and a long hydrocarbon chain of 15 to 17 carbons, designated as 19.
Additionaliy, the quaternary ammonium compounds are designated with the tallow tails 17, consisting of 16 to 18 carbons. Some of the quaternary am~nium compounds contain a benzyl compound 21 and one alkyl chain and two methyl groups, while the other quaternary ammonium com-pounds consist oF two alkyl hydrocarbon chains 1/ and two .
,, - .
, ' ' ' ~28~ 3 methyl groups. The van-der Waal bonding of the hydro-carbon chain 19 of the urushiol compound 18 is dia~ram-matically shown with the long-chain alkyl group l7 of the organophilic clay ]5. Additionally, i~ is felt th~t the phenyl group 20 of the urushiol compound may have some affinity for the active surface of the platelet 1~
of ~he organophilic clay. This is shown diagramma~ically in the right-hand portion of Fig. ~.
It should be un~erstood that this explanatiotl is som~what hypothetical. However, it ;s support~d by data, as will hereinafter be shown. The fact of the matter is that adsorption apparently is not the major mechanism itl ~his instance, since materials with higher surface areas do not provide the protection that is provided by the organo-treated clays~ It ~s felt, the~efore, that the organic surface area is of major importance while the inorganic surface area formed by the pores oE t~e clay platel~s per~orm only a secondary function r~lativ~
to ~he absorp~ive function performed by th~ r~ctive tallow tails of the organophilic clays.
T~e invention will be better understood by rererence to the examples contained hereinafter.
In the following examples, reference is made to Sure~
deodorant and DrysolTM, both of which contain the antiperspirant aluminum chlorohydrate.
IThe Sur ~ antiperspirant, in the spray form, contains aluminum chlorohydrate, cyclomethicone, ~uaternium-18 hectorite, per~ume, ethanol, isobutane and propane. This composition is reported to contain from 1 to 5~ guaternium-18 hectorite. See, for example~ Clinical Toxicoloq~ of Commercial Products, Gosselin, et al, 5th edition, William and Watkinsr 1984, PV-633.
B
.
.
, . .
~2~ '73 -13a-Quaternium-18 hectorite is a reaction product of hectorite and ~uaternium-18 is commercially availa~le as Bentone 38 (NL Chemicals). Quaternium-18 (CAS Number 61789-80-8) is predominantly (90 to 100%) a quaternary salt that conforms generally to the formula:
CH3 ~
R C - R Cl where R represents hydrogenated tallow fatty radicals.
~ uatern~um-18, quaternium-18 hectorite and quaternium-18 bentonite are generally considered safe as cosmetic ingredients and have been widely used as suspending agents for antiperspirants. See ~Final Report on the Safety Assessment of Quaternium-18, Quaterniu~-18 ~ectorite, and Quaternium-18 Bentonite," ~ournal Qf the ~merican ~ollQae of ~oxic~looY, Vol. 1(2), 1982, pp. 71-83.
.
_ -14-~XAMPLF, 1 A batch of organophilic clay is prepared by admixing finely milled sodium bentonite with sufficient quaternary ammonium compound ~o as to provide 8S ~illiequivalents of quaternary ammonium compound per 100 grams of clay. The quaternary ammonium compound i~ obtained from hydrogenated tallow and contains two alXyl groups containing from 16 to 18 carbons in length and 2 methyl groups. This is commonly referred to as quaternium-18. The quaternary ammonium compound was mixed with su~ficient water and the sodium bentonite so as to produce a slurry containing about 4~ by weight of clay. The temperature of the slurry was maintained at 170 for a period of about 30 minutes. This allowed the quaternary ammonium compound to ion exchange with the clay particles. The ~lurry was then ~pray dried i~to a fine powd r. This product ~ 6 known in the cosmetic industry as quaternium-18 bentonite. The powdered organo-clay was admixed with about 4.3~ by weight of an SD-~0 alcohol and about 84% by weight of cyclomethicone (Dow-Corning 344~ as a Yehicle. This then produced a gel containing 11. 3~ oxgano-clay, 84% cyclomethicone and 4.3~ SD-40 alcohol. The gel was then loaded into an aerosol container at room temperature. A valve assem~ly was ~nserted into thè container and the val~e was crimped. An A-46 mixed hydrocarbon propel}ant was then introduced through the valve assembly under pressure to produce an aerosol composition within the can of 30:70 weight ratio o~
gel to propellant. The A~46 propellant is 84% isobutane and 16% propane by weight and has a vapor pressure of 46 psig at 70~F.
,~
B
.
~2~
-14a~
EXAMPLE _ The test procedure* involved the application of Sure~
deodorant as a comparison composition and the organophilic clay of Example 1, spray applied to the skin of the forearm at 1, 4 and 24 hours before the application of dilutions of purified urushiol in acetone in a double-blind fashion. Three samples of urushiol in acetone were made up with five microliters of urushiol in acetone, ranging i~ amount from .25ug to .OOSug. The samples of urushiol in ac'etone were then applied to the patch test sites. The p~tch test sites were thereafter read two to five days later and recorded from N to 4 as follows:
N = Normal 1 = Erythema and edema involving half the test. site 2 = Erythema and edema plus small vesicles involving the entire site 3 = Full involvement of the test site with erythema and ed~ma and large vesicles 4 = Bullae ~ -A -1 score equals a de~inite positive reaction which in-volves less than 1/2 of the test site and a ~ equals a questionable reaction which either is subsequen~ly read as + or *T~ese tests were conducted under a grant from the U.S.
Forestry Service under the supervision of Dr. William Epstein of the University ~f California Medical School at San Francisco.
~' :
. ~
' ~ ~
~' ~
A second preliminary study was car~ied QUt, com~
paring the results of pretreatment wit~ Sure~ to pre-treatment with Drysol~ (a 20% w/v concentrate of 5 aluminum chloride he~ahydrate in alcohol). The pre-treatment time was 4 hours. The patch tests were urushiol and the patch test readings were the same as described above.
EXAMPLE _ In the next series of experiments, the subjects were pretreated with breakdown products of Sure~ that either were missing the aluminum ,chlora,lhydrate or the suspending agents (hectorite and propylene carbonate).
The patch tests with urushiol and the patch test readings 15 were the same as described above.
The results of these tests are shown in Table I, T~BL~ I
Average Protective Effect of SURE~ and Example 1 Compared to the Control 20 Pretreatment ' ' Time'' Mi'c'rogr'a'm'Di'lut'i'o'n's''o'f'Urush'i'ol .
l hour 0.25 '0'.1 '0'.'05 '0'.'025 Sure~ 1 1.3 ,1.2 ,1.0 Example 1 N o t D o n e 25 4;hours Sure~ 1.5 0.9 0.9 0.5 ' Example 1 3.0 2.0,1.8 1~3 -~
24 h'ours Sure~ 0 0.751.0 0.4 30 Example 1 1.5 0.9 0.9 1.5 Table I shows that pretreatment with the Sure~
deodorant does reduce the pat,ch test reaction to dilu-tions of urushiol. However, Sure~ is not able to com-pletely prevent the reactions, but simply reduce them.
35 The material of Example 1, on the other hand, was more : , . . .
- , . ~ .
. ;; . '. ~ ~; ' . .
:. . . .
'7 -16~
effective at reducing the reactions and this was par-ticularly noticeable at 4 and 24 hours after applicatio~s, as compared to Sure~. This table a~erages overa~l responses.
The preliminary study9 comparing the high concen-tration of the aluminum salt (Drysol~) to Sure~, indi-cated that the alcoholic solution was less effective than Sure~.
Another experiment compared the blocking effect of 10 Sure~ with its ingredients, i.e. without fillers and without aluminum chloralhydrate. In one instance, Sure~
was compared to the aluminum compound containing prep-aration without the fillers, i.e. ~he organophilic hectorite, and the two were equal on two occasions.
15 Sure~ was more effective in one and definitely more effective in four instances. In no instance was the aluminum salt more effective than Sure~. Sure~, con-; taining only the fillers and no aluminum was compared to Sure~ and the two preparations were e~ual on two 20 occasions. Sure~ was more effective than the fillerpreparations on two occasions and much more effec~ive on one occasion. On the other hand, the filler was more effective than Sure~ on two occasions. Finally, in direct comparison of the filler versus the aluminum 25 preparation, the filler was more effective than the aluminum salt on two occasions and much more effective in four additional trials. In one instance, the aluminum ; salt was more efEecti~e than the filler preparations.
The tests, as previously described, were carried out with three particularly sensitive individuals.
These are shown in Tables II, III and IV.
As can be seen, a~ter the second day, the control showed a normal reaction for the patch test for the low 35 concentrations, but a 2 reaction as to any concentration ~. .
.: - . .
:
..
: .
:
TABIE II
4 hours after application Day 2 Day 4 Reg.
Urushiol Control Sure~ Ex. 1 Con~rol Sùre~ Ex. 1 .25 2-1 N 3 3 N
.1 21 N 2 1 N
.05 2'N N 2 N N
.025 NN N N N N
.01 NN N N N N
24 hours after application 'Day 2 ' Day 4 Reg.
Urushi'ol Contr'ol 'Sure~ Ex. 1 'Cont'rol' S'ure~ E'x.' 1 .25 21 N 3 3 .l 21 N 2 .05 2N N 2 N N
.025 NN N N N N
.01 NN N N N N
,. , . : .
.
, ' ' .. .. .
.
` TABLE`'III
4 hours after application ''Day 2 ''Day 4 Reg.
S Urushiol 'Con'trlol `Sure~ ` Ex.` 1 ''Co`nt'rol''S`ure~''EX.',l .25 ~1 2 2 N 4 2 N
.05 2 2 N 3 2 N
.025 1 -1 N 2 1 N
.01 -1 N N N N N
24 hours a~ter application Day 2 ''Day 4 Reg. ~ , Urushiol Control Sure~ EX. 1 ~Control':Sure~ EX. 1 .25 .1 2 2 2 4 2 2 .05 2 2 2 3 2 2 .025 1 1 N 2 1 N ,~
.01 -1 N N N N N
'.
:
- : . .: :
:
,~ . .
- . ~
: . ' ' , " ~ ':
.
.~ . . . .
, ''T~B~E'IV
4 hours after application Day 2 ''Day 4 Reg.
Urus'hiol Control Su`re~''EX. 1 ` Con'trol' Sure~ Ex.' 1 .05 2 2 N 3 2 -1 .025 N N N 1 N N
.01 N N N N N N
24 hours after application Day 2 `':a'y'4 Uru_hiol Control' Sure~''EX.' 1 Con~rol' Sur'e~ 'Ex` 1 .05 2 1 1 3 2 2 .025 N -1 N 1 N N
.01 N N N N N N
i . ~. ~ ' ' ' . . . ' '- '.
~. ~ . : , ` ' `
, : ` ;. ' ,' ' , ' of urushiol above .05 micro~rams. Sure~, on the other hand, provided some protection at .05 micrograms and reduced the size of the reaction as to the concentra-tions above .l. The material of Example l, however, 5 showed full protection 4 hours after application for all concentrations of the material. Essentially the same results were obtained after Day 4. Except with the control, the severity of the reactions increased. The severity of the reaction of the high concentration of 10 urushiol increased with the Sure~ application, but the material of Example 1 gave full protection throughout the total range o-f concentration. 24 hours after appli-cation, essentially the same results were obtained on Day 2. On Day 4, the severity of -the reaction was 15 greater with the control and with the Sure~ sample and there was a 1 range of reaction for the Example 1 material after 24 hours.
Table III, for a completely different individual, who was extremely sensitive, demonstrated a more severe 20 reaction with both the control sample and the Sure~
sample, after Day 2 and Day 4, as compared to Table II.
However, the organophilic clay of Example 1 provided good protection, both for Day 2 and Day 4 throughout the entire range of urushiol concentrations. The 25 severity of the reactions increased across the board after application and e~en the material of Example 2 s~owed a moderate grade 2 reaction for the higher con-centrations a~te~ the second and fourth days. The superiority of the material of Example 1 over the control 30 and over the Sure~ is shown, however, throughout.
Table I~ demonstrates in like manner the protection afforded by the individual throughout a smaller range of urushiol concentrations. After the fourth day, from 4 hours after application, the material of Example 1 showed 35 a positive reaction, as indicated by -1. In like manner, ~
~:
-, - ' ~ ' : .
~A~1:3~ ~
the table demonstrates that even 24 hours a~ter appli-cation, there is protection against the low concentrations of urushiol by the organophilic clay of Example l on the second and fourth days following application.
A series of other over-the co~mter preparations, Technu~, Less Ivy~, and Off~, were completely ineffective in protecting the skin from the ef~ects o:E urushiol.
It is believed that the long Cl8 chain ofthe urushiol molecule is absorbed through van-der Waal forces with lO the long, Cl6 to C22 carbon tallow tails of the organo-philic clays. Additionally, it is ~elt that the phenyl group of the urushiol may have some affinity for the active surface of the clay platelet itself. The material may be applied in aerosol form, as a salve, or as a 15 stick, onto the skin, prior to encountering the urushiol-producing plants, such as poison ivy, oak or sumac. The comparative study, however, has clearly sho~n that the organophilic clays of this invention are more effective than any material heretofore known in the prevention of 20 experimentally-induced poison oak or ivy dermatitis.
Many modifications will occur to those skilled in the art from the disclosure, which is meant to be non-limiting except so as to be commensurate in scope with the appended claims.
Claims (18)
1. An aerosol allergen barrier composition for topical application comprising:
A. a barrier composition comprising 1) from about 5 % to about 15 % by weight of a smectite clay having an ion exchange capacity of at least 50 milliequivalents per 100 grams, said clay having been ion exchanged with at least 50 milliequivalents per 100 grams of said clay of a quaternary ammonium compound having at least one alkyl group containing more than 10 carbon atoms, and
A. a barrier composition comprising 1) from about 5 % to about 15 % by weight of a smectite clay having an ion exchange capacity of at least 50 milliequivalents per 100 grams, said clay having been ion exchanged with at least 50 milliequivalents per 100 grams of said clay of a quaternary ammonium compound having at least one alkyl group containing more than 10 carbon atoms, and
2) from about 95 % to about 85 % by weight of a pharmaceutically acceptable non-toxic vehicle; and B. an aerosol propellant 2. The aerosol composition of Claim 1 comprising from about 10 to 50 parts by weight of said barrier composition and about 90 to 50 parts by weight of said aerosol propellant.
3. The aerosol composition of Claim 1 wherein said smectite clay is a highly activated clay.
4. The aerosol composition of Claim 1 wherein said vehicle is a long chain fatty acid ester.
5. The aerosol composition of Claim 1 wherein said vehicle is a silicone fluid.
6. The aerosol composition of Claim 1 wherein said quaternary ammonium compound is quaternium-18.
7. The aerosol composition of Claim 1 wherein said ion exchanged smectite clay is quaternium-18 bentonite.
8. The aerosol composition of Claim 1 wherein said ion exchanged smectite clay is quaternium-18 hectorite.
9. The aerosol composition of Claim 1 additionally comprising a low molecular weight polar organic activator for said smectite clay.
10. The aerosol composition of Claim 9 wherein said activator is propylene carbonate.
11. The aerosol composition of Claim 9 wherein said activator is a short chain alkanol.
12. A method of preventing contamination of clothes and utensils with an allergen comprising applying to said clothes and utensils a barrier composition consisting essentially of (1) from about 5% to about 15% by weight of a smectite clay having an ion exchange capacity of at least 50 milliequivalents per 100 grams, said clay having been ion exchanged with at least 50 milliequivalents per 100 grams of said clay of a quaternary ammonium compound having at least one alkyl group containing more than 10 carbon atoms, and (2) from about 95% to about 85% by weight of a pharmaceutically acceptable non-toxic vehicle.
13. The use of a carrier composition comprising (1) from about 5% to about 15% by weight of a smectite clay having an ion exchange capacity of at least 50 milliequivalents per 100 grams, said clay having been ion exchanged with at least 50 milliequivalents per 100 grams of said clay of a quaternary ammonium compound having at least one alkyl group containing more than 10 carbon atoms, and (2) from about 95% to about 85% by weight of a pharmaceutically acceptable non-toxic vehicle for protecting the skin from contact with an allergen.
14. The use of claim 13 wherein said barrier composition further comprises a polar activator for said smectite clay in a proportion of from about 1% to about 4% by weight.
15. The use of claim 13 wherein said ion exchanged smectite clay is quaternium-1% bentonite.
16. The use of claim 13 wherein said ion exchanged smectite clay is quaternium-18 hectorite.
17. The use of claim 13 comprising the additional step of manually stroking the area of the skin to which said barrier composition has been applied, whereby platelets making up the structure of said clay are oriented to lie parallel with the surface of the skin.
18. The use of claim 13 wherein said barrier composition is applied by spraying.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US78516785A | 1985-10-07 | 1985-10-07 | |
US785,167 | 1985-10-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1289073C true CA1289073C (en) | 1991-09-17 |
Family
ID=25134643
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000519891A Expired - Lifetime CA1289073C (en) | 1985-10-07 | 1986-10-06 | Allergen absorbent and blocking gel |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0219054B1 (en) |
AT (1) | ATE74520T1 (en) |
CA (1) | CA1289073C (en) |
DE (1) | DE3684752D1 (en) |
ES (1) | ES2033668T3 (en) |
GR (1) | GR3005057T3 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5869033A (en) * | 1996-04-12 | 1999-02-09 | Enviroderm Pharmaceuticals,Inc. | Method of preventing skin irritation caused by fecal enzymes |
EP2052715A4 (en) * | 2006-08-09 | 2013-02-20 | Shiseido Co Ltd | Sol composition containing organomodified clay mineral having flaky particle structure, oil-base gel compositions and w/o emulsion compositions containing the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2684321A (en) * | 1950-09-28 | 1954-07-20 | Rohm & Haas | Skin treating ion exchange mixture |
US2857311A (en) * | 1954-07-06 | 1958-10-21 | Rohm & Haas | Dermatological mixture of ion-exchange resins |
US3922342A (en) * | 1973-05-07 | 1975-11-25 | Univ Minnesota | Poison ivy and poison oak treatment utilizing hydrophilic anion exchange material |
US4350605A (en) * | 1977-11-22 | 1982-09-21 | Peterson/Puritan, Inc. | Water-in-oil emulsions |
-
1986
- 1986-10-06 CA CA000519891A patent/CA1289073C/en not_active Expired - Lifetime
- 1986-10-07 DE DE8686113910T patent/DE3684752D1/en not_active Expired - Lifetime
- 1986-10-07 ES ES86113910T patent/ES2033668T3/en not_active Expired - Lifetime
- 1986-10-07 AT AT86113910T patent/ATE74520T1/en not_active IP Right Cessation
- 1986-10-07 EP EP86113910A patent/EP0219054B1/en not_active Expired
-
1992
- 1992-06-30 GR GR920401389T patent/GR3005057T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
EP0219054B1 (en) | 1992-04-08 |
ATE74520T1 (en) | 1992-04-15 |
DE3684752D1 (en) | 1992-05-14 |
EP0219054A3 (en) | 1988-01-27 |
EP0219054A2 (en) | 1987-04-22 |
ES2033668T3 (en) | 1996-07-16 |
GR3005057T3 (en) | 1993-05-24 |
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